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Study of an Unrefined Humate Solution as a Possible Attenuation-based Remedy for Uranium Contamination in Acidic Groundwater - 20351

The Savannah River Site (SRS), joined the environmental cleanup program in 1981 after the Cold War, and was designated as a hazardous waste management facility. About 1.8 billion gallons of acid wastes were disposed into the F/H Area Seepage Basin that included many radionuclides and dissolved metals, resulting in highly contaminated groundwater plumes with pH of 3 - 5.5. The acidity of the plumes contributes to the mobility of several constituents of concern (COC) such as H-3, U-238, I-129, and Sr-90 for the F-Area plume and H-3, Sr-90 and mercury for the H-Area plume. An active treatment (pump-and-treat and re-injection) system was constructed and put in place in 1997 to address the removal of metals and radionuclides from the contaminated groundwater. As remediation projects advanced, active treatments were transitioned to more passive or enhanced-passive approaches such as the subsurface barrier with base injection system, which has been controlling the mobility of contaminants. However, new and more efficient attenuation-based remedies are always sought. Several studies have proposed that humic substances can be used to remediate sites contaminated with heavy metals by creating a permeable reactive barrier. Humic substances (HS) are major components of soil organic matter. HS are polyfunctional organic macromolecules formed by the chemo-microbiological decomposition of biomass or dead organic matter. These substances are usually divided into three main fractions: humin (insoluble at all pH values), humic acid (soluble at pH greater than 3.5), and fulvic acid (soluble at all pH values). Humic substances are major components of the soil at SRS and, in addition, are also helpful in the removal process of uranium. This research focuses on uranium (VI), which is a key contaminant of concern in the F-Area groundwater plume. The interaction of uranium with sediment in the presence or absence of humic substances involves complex mechanisms that are not yet well understood. The interaction of U(VI) with humic substances can affect the adsorption of U on sediment, altering its mobility in the subsurface. The objective of this study is to study the mobility of uranium in the presence of humic acid and to determine if sediments amended by humic acid can enhance the sorption of heavy metals onto sediments. In this research, experiments were conducted using background (clean) F-Area aquifer sediments to understand and predict uranium mobility. A blended material, humate, containing both humic and fulvic acids and a chemically modified humate (KW15 modified humic or mod-HA) was studied as a possible amendment for uranium remediation in SRS groundwater. Batch experiments were conducted in triplicates using 20 ml of aqueous suspension in DI water containing SRS sediment and mod-HA and studied the effect of pH, kinetics of humate sorption onto SRS sediment and also studied the sorption of uranium onto mod-HA amended SRS sediment. Results indicate that mod-HA amended sediment increases uranium removal significantly. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Interim Measures Work Plan: South Repeater Building: Solid Waste Management Unit 121: Hydraulic Containment and Groundwater Treatment System for Per- and Polyfluoroalkyl Substances: Kennedy Space Center, Florida

This document presents the design details of a granular activated carbon (GAC) hydraulic containment and groundwater treatment system Interim Measures Work Plan for the South Repeater Building site (South Repeater, Solid Waste Management Unit 121), located at John F. Kennedy Space Center (KSC), Florida. The interim measures (IM) treatment area includes the source area and downgradient property boundary, which have been impacted by per- and polyfluoroalkyl substances (PFAS). The objectives of the IM are to treat the source area and mitigate PFAS migration to areas outside of KSC boundaries. This document was prepared by AECOM Technical Services, Inc., for the National Aeronautics and Space Administration under Contract 80KSC019D0010, Task Order 80KSC021F0096. The IM consists of the installation and operation of 19 extraction wells and an associated groundwater treatment system. A total of 13 wells will be installed to a depth of 34 feet below land surface (bls) to target the upper medium-grained sand with shell layer. A total of six wells will be installed to a depth of 56 feet bls to target the lower layer of poorly graded sand with shell fragments. The system will be designed to operate each extraction well simultaneously using submersible pumps at flow rates of 5 or 10 gallons per minute (gpm), excluding one extraction well with a flow rate of 30 gpm. The extracted groundwater will be conveyed to a groundwater treatment system, where it will be treated via GAC prior to disposal via infiltration. To evaluate treatment system performance, baseline groundwater sampling will be conducted prior to treatment system startup. Performance monitoring will be completed quarterly for the first year. A total of eight performance monitoring wells will be installed to a depth of 12 feet bls, and eight performance monitoring wells will be installed to a depth of 30 feet bls. In addition to the installation of 16 performance monitoring wells, 12 existing monitoring wells will be incorporated into the performance monitoring program.

groundwater treatment↗

Characterization of Spent Purolite A530E Resin with Implications for Long-Term Radioactive Contaminant Removal

Direct removal of pertechnetate anion (TcO4-) from the subsurface contaminated plumes at legacy nuclear weapons production sites, is effective remediation strategy to prevent their spread to adjacent aquifers but is also challenging because TcO4- is a trace component of the contaminated groundwater typically containing large access of other anionic constituents, such nitrate, sulfate, chloride and others. It can be achieved through ion exchange treatment using Purolite A530E resin which to date however has only been evaluated under laboratory conditions and many questions regarding its long-term operational performance remain. To address this need, here we report comprehensive characterization of the spent Purolite A530E resin which processed over 5.38x109 L of contaminated groundwater and successfully removed about 3.78 Ci of Tc-99 during four years of operation at the 200 West Pump & Treat facility at the US DOE Hanford site. This Tc-99 loading constitutes however only about 0.034% of the theoretical capacity of the resin which retained significant amounts of sulfate. Among other radioactive contaminants, small quantities of U-238, Co-60, and I-129 were retained by the resin. The total loading of iodine (combined 1-127 and I-129) on the spent resin exceeded that of Tc-99. To elucidate the mechanism of iodine retention, ion exchange behavior of iodide and iodate was investigated. Purolite A530E resin exhibited highly efficient uptake of iodide and only moderate affinity for iodate in accord with their Gibbs energy of hydration. Sorption isotherms for both anions obeyed Freundlich model.

Levitskaia, Tatiana G.↗

Review: “Jacob’s Zoo”—how using Jacob’s method for aquifer testing leads to more intuitive understanding of aquifer characteristics

The interpretation of aquifer responses to pumping tests is an important tool for assessing aquifer geometry and properties, which are critical in the assessment of water resources or in environmental remediation. However, the responses of aquifers, measured by time-drawdown relationships in monitoring wells, are nonunique solutions that are affected by many factors. Jacob's Zoo is a collection of graphical interpretations that allows students and practitioners to develop an intuitive feel for how natural hydrogeological systems work, and develop a set of skills that provide a better understanding of aquifer properties much beyond interpretation of pumping tests. Jacob's Zoo, based on the work of Jacob (1950), fosters a deeper understanding, although few practitioners realize the full utility of the method. Jacob CE (1950) Flow of groundwater, In: Rouse H (ed) Engineering Hydraulics, Wiley, New York. P 321-386.

54 ENVIRONMENTAL SCIENCES↗

Launch Complex 34, SWMU Cc054 2021 DNAPL Source Zone Operations, Maintenance, and Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ) and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 12 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. Site-wide biennial LTM sampling was not conducted during this reporting period and is scheduled to be conducted in December 2022. The timeframe for activities documented in this PMR extends from April 1, 2021 to March 31, 2022. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the DSZ and deep dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to re-characterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS to more adequately capture residual contaminant mass. The operational period for Year 12 of the HCS was from April 1, 2021 to March 31, 2022. Operational runtime for the system was 94 percent during Year 12, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2022, a total of 285,712,801 gallons of groundwater containing 84,933 pounds of VOCs have been removed by the HCS. Influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 12,000 µg/L (March 2022). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2021 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events in 2017, 2018, 2019, and 2020. Full vertical profile sampling was completed at each DPT from 8 to 98 ft bls, at 5 foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations at depths ranging from 8 to 98 ft bls. An overall increasing trend of TCE concentrations was observed in DPT samples during this reporting period, which may be due to several recovery wells that were turned off during the AS Pilot Study in the DSZ that operated from July 2021 to February 2022 (documented separately from this report). The maximum TCE concentration in 2021 was 15,400,000 µg/L in the 58 ft bls depth interval at DPT597 (previous maximum result in 2020 was 1,690,000 at 48 ft bls at DPT596). During the 2021 DPT event, the overall majority of TCE contamination was identified in the 58 ft bls interval (below Layer 4), where in the previous year the majority of mass was observed in Layer 4. This trend appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, monitoring well samples were collected from deep wells in the DSZ area (Layers 7 and 8) to verify vertical delineation. All monitoring well results were non-detect or below cleanup levels, with exception of one well (IW0162, screened 105 to 115 ft bls, which is below the existing recovery well capture zone) where TCE was identified above cleanup target levels. The HS 6 AS system remained operational during the reporting period covered under this report. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual prior to this operational period. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2021 show concentrations of contaminants of concern (cis-1,2-dichloroethene, trans-1,2- dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. Overall, the tasks associated with Year 12 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with the recommendations of the 2020 LC34 (Year 11) Operations, Maintenance, and Monitoring Report for DNAPL Source Zone, Site Wide LongTerm Monitoring, and Hot Spot 6 Air Sparging System PMR (NASA, 2021c). Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.

trichloroethene↗

Launch Complex 34, SWMU CC054 2023 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring and Phase Two Expansion Construction Completion Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 14 operations and performance monitoring of the hydraulic containment (HC) Interim Measure (IM), details associated with construction and implementation of the HS 6 AS system expansion (Phase Two), and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. The timeframe for activities documented in this PMR extends from April 1, 2023 to March 31, 2024. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the shallow and deep DSZ and surrounding dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to recharacterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS and install additional recovery wells in Layer 7 to more adequately capture residual contaminant mass. The operational period for Year 14 of the HCS was from April 1, 2023 to March 31, 2024. Operational runtime for the system was 94 percent during Year 14, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2024, a total of 344,849,634 cumulative gallons of groundwater containing 94,656 pounds of chlorinated volatile organic compounds (CVOCs) have been removed by the HCS. During the reporting period covered under this report, the HCS recovered 31,176,393 gallons and approximately 6,319 pounds of CVOC mass. Total combined influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 25,000 µg/L (March 2024). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in January 2024 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2022. Full vertical profile sampling was completed at each DPT from 8 to 98 feet below land surface (bls), at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 28 to 98 feet bls. An overall decreasing trend of TCE concentrations was observed in DPT samples during this reporting period, which is a reduction from the previous event (December 2022) and the peak event in December 2021, where TCE percentages appeared to increase in all depth zones because several recovery wells were turned off during the AS pilot study in the DSZ. The maximum TCE concentration in January 2024 was 1,600,000 µg/L in the 53 feet bls depth interval at DPT594 (previous maximum result in 2022 was 1,800,000 µg/L in the 48 feet bls depth interval at DPT599). This maximum concentration in the 53 feet bls depth interval is in the deep capture zone. During the January 2024 DPT event, the largest portion of TCE mass was observed in the 48 feet bls interval above/within Layer 4. This trend remains consistent with previous years and appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, annual groundwater samples were collected from 11 deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2023 to verify vertical and horizontal delineation. Three of the wells were also sampled biweekly to evaluate operations of recovery well RW21D (screened 86 to 106 feet bls), which was installed in January 2023. Of the Layer 7/8 monitoring sampled only annually, results were non-detect or less than groundwater cleanup target levels GCTLs in December 2023, with the exception of one well, IW45D2, which had a cis-1,2-dichloroethene (cDCE), detection greater than the GCTL. Of the three wells sampled biweekly during the operational period, the well located closest to Layer 7 recovery well RW21D (IW44D2, screened 105 to 115 feet bls) had concentrations of TCE, cDCE and vinyl chloride (VC) greater than GCTLs throughout the operational period, but displayed a decreasing trend since the peak concentrations in September 2023. The maximum TCE concentration during this operational period was 190,000 µg/L at IW44D2 in September 2023, but reduced to 700 µg/L in March 2024, indicating the HCS is still effectively removing mass from the source area. Expansion of the HCS and addition of new recovery wells is ongoing and will continue to be evaluated as the groundwater recovery scheme is optimized. Details of the expansion and optimization will be provided in a future PMR. The HS 6 AS IM was initiated in 2018 with 160 AS wells and expanded in 2019 with another 140 AS wells. An additional expansion of the HS 6 AS IM was completed during the reporting period covered under this report and details of the construction implementation and startup of the expansion are detailed in Section III of this report. The new expansion, referred to as Phase Two, was implemented between August 17, 2022 and August 28, 2023, and included the installation of 190 air sparge wells to treat an additional 11.2 acres. The original configuration (referred to as Phase One) operated until Phase Two came online, then all but 52 AS wells were turned off so the components could be moved and utilized in the Phase Two area. The 52 AS wells that remain on are in a barrier configuration preventing contaminated groundwater from impacting the treated area. The HS 6 AS system (both Phase One and Two) operated normally during the reporting period covered under this report. Semi-annual performance monitoring of the Phase One configuration was conducted in April and November 2023, consistent with previous years. For the Phase Two configuration, 21 new monitoring wells were installed and sampled quarterly, with a baseline event in July 2023, and quarterly events in November 2023 and February 2024 summarized in this report. Semi-annual monitoring results collected in April and October 2023 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and VC) have decreased to less than GCTLs in nearly all wells and not impacting the surface water drainage canal, indicating the HS 6 IM continues to meet objectives. The baseline and quarterly sampling for the Phase Two configuration indicate generally decreasing concentrations in wells within and around the perimeter of the treatment area. At least two more quarters of monitoring will be conducted and once those results are evaluated a reduced the sampling frequency may be considered. Overall, the tasks associated with Year 14 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with recommendations included in the previous 2022 LC34 (Year 13) PMR. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.

groundwater remediation↗

Regulatory and Technical Issues Concerning the Detection and Treatment of NDMA-Contaminated Groundwater at NASA WSTF

The National Aeronautics and Space Administration (NASA) White Sands Test Facility (WSTF) was established in 1963 primarily to provide rocket engine testing services for several NASA programs. The groundwater underlying the site has been contaminated as a result of historical operations. Groundwater contaminants include several volatile organic compounds (VOCs) and two semi-volatile compounds: N-nitrosodimethylamine (NDMA) and N-nitrodimethylamine (DMN). This paper discusses some of the technical, analytical, regulatory, and health risk issues associated with the contaminant plume. The plume has moved approximately 2.5 miles downgradient of the facility industrial boundary, with evidence of continued migration. As a result, NASA has proposed a pump and treat system using air strippers and ultraviolet (UV) oxidation to stabilize future movement of the contaminant plume. The system has been designed to treat 1,076 gallons (4,073 liters) per minute, with provisions for future expansion. The UV oxidation process was selected to treat NDMA-contaminated groundwater based on successes at other NDMA-contaminated sites. Bench- and pilot-scale testing of WSTF groundwater confirmed the ability of UV oxidation to destroy NDMA and generated sufficient data to design the proposed full-scale treatment system. NDMA is acutely toxic and is a probable human carcinogen. EPA-recommended health risk criteria for the residential consumption of NDMA/DMN-contaminated groundwater was used to determine that a 1.0 x 10(exp -6) excess cancer risk corresponds to 1.7 parts per trillion (ppt). EPA analytical methods are unable to detect NDMA and DMN in the low ppt range. EPA's current Appendix IX analytical method used to screen for NDMA, Method 8270, can detect NDMA only at levels that are orders of magnitude greater than the recommended health risk level. Additionally, EPA Method 607, the most sensitive EPA approved method, has a detection limit of 150 ppt. This corresponds to an excess cancer risk of 9.0 x 10(exp -5), which exceeds the State of New Mexico's water quality standard of a cancer risk less than 1 x 10(exp -5). The treatment system has been engineered to treat contaminated groundwater to levels significantly below the New Mexico standard. However, the inability of EPA-approved analytical methods to detect NDMA and DMN at low ppt levels, and to provide verification of compliance with the 1 x 10(exp -5) cancer risk, introduces a notable risk to the long-term operation of the system. WSTF has been working with Southwest Research Institute to develop a non-EPA analytical method that can achieve a reporting limit of 1 ppt, which corresponds to an excess cancer risk of 7.6 x 10(exp -7). WSTF is currently developing a proposal to obtain approval from the New Mexico Environment Department (NMED) of this non-EPA method.

Wiebe, D. T.↗

Predicting future well performance for environmental remediation design using deep learning

Here in this study, we developed a deep learning (DL) framework with a multi-channel three-dimensional convolutional neural network (MC3D-CNN) to predict well performance and thereby assist future environmental remediation design. Such prediction of extraction well performance at designated locations is critical for configuring pump-and-treat (P&T) well network design and operation, setting reasonable target closure dates for overall remedying, and estimating remedy costs. The framework is developed with operational and monitoring data routinely collected during P&T remedy operations, including well extraction and injection rates as well as in situ contaminant concentrations. Traditionally, the collected data were rarely used for purposes other than assessing past well performance and the accuracy of the conceptual site model. However, recent advances in data-driven computational approaches enable better use of the large datasets to inform future well performance, enhance site characterization, and improve remediation planning. In this study, we established a DL framework to integrate transient three-dimensional contaminant plumes and multiple aquifer properties (e.g., hydraulic conductivity and hydrostratigraphic maps) to identify characteristic patterns controlling and representing extraction well mass recovery, aiming at providing future mass recovery estimates for existing wells and candidate wells at any proposed locations. We evaluated our framework by using a realistic synthetic dataset generated from a well-calibrated flow and transport model used in the 200 West Area of the U.S. Department of Energy’s Hanford Site in southeastern Washington state. The multi-channel feature in our framework allows integration of various types and temporal densities of training datasets for DL model development. Overall, we found that the trained DL model achieved an accuracy of over 90% in ranking extraction well performance in validation datasets, and over 80% in predicting high-performance-ranking well locations. This data-informed approach provides a flexible tool to support adaptive site management, streamline decision-making, and potentially reduce remediation time and costs. Our DL framework can be used as a filtering tool to improve the current P&T network optimization design by reducing the number of candidate well locations.

54 ENVIRONMENTAL SCIENCES↗

Reduction and potential remediation of U(VI) by dithionite at an in-situ recovery mine: Insights gained by δ 238 U

In-situ recovery is a common method of mining U ore. This technique involves injecting an oxidant to oxidize U deposited as insoluble U(IV) to soluble U(VI) and a complexing agent to form mobile U(VI) compounds, which are extracted from mining waters. Unfortunately, U concentrations often remain elevated in groundwater following this mining process. One promising technique to decrease U concentrations to acceptable levels is in-situ remediation where a reductant is injected into the mined area to reduce U(VI) back to insoluble U(IV). Here we assess the efficacy of the chemical reductant dithionite to reduce U(VI) concentrations. While dithionite can reduce environmental Cr(VI), dithionite has previously never been tested for reducing U(VI) in the environment. We determine how effectively dithionite remediates U(VI) contamination using aqueous U concentration and δ 238 U data. U concentrations and δ 238 U decrease during the dithionite experiment, demonstrating that dithionite induces U(VI) reduction. As dithionite is removed by pumping, U concentrations and δ 238 U increase towards background levels, but U(VI) reduction continues for an extended period. In conclusion, measurements demonstrate that re-oxidation and remobilization does not appear to occur due to the reducing condition of groundwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative performance assessment of air-source and ground-source heat pumps using CO₂ and R-410A with water well integration: A simulation study

This study investigates the performance and feasibility of heat pump systems for residential space heating in cold climates, with a particular focus on ground source heat pumps (GSHPs) with water wells. Four configurations are modeled and compared, a CO 2 air-source heat pump (ASHP), an R-410A ASHP, a CO 2 GSHP with water well integration, and an R-410A ground-source heat pump with water well integration. System simulations are conducted at both equipment and whole-building levels, followed by a nationwide analysis across ten representative cities using EnergyPlus. Results show that water-well-coupled GSHPs maintain approximately 87 % of their efficiency and 85.5 % of heating capacity as ambient temperature drops from 47 °F/8.3 °C to −15 °F/-26.1 °C, whereas ASHPs retain only 55 % efficiency and 44.5 % capacity. R-410A systems achieve higher efficiency, while CO 2 systems provide significant environmental advantages, including reduced risks of groundwater contamination from refrigerant leakage. On average, the CO 2 GSHPs deliver 35–45 % heating energy savings relative to ASHPs and demonstrate strong potential as a replacement for gas furnaces in cold climates. This work represents a systematic comparative assessment of CO 2 and R-410A air-source and ground-source heat pumps with water well integration. In conclusion, the findings highlight the technical viability, environmental benefits and deployment potential of CO 2 GSHPs, offering a pathway toward efficient and sustainable residential heating solutions in diverse U.S. climates.

CO 2 GSHP↗

The Use of Silver Chloride Injection in Remediation of Iodine-129 by In Situ Capture as Silver Iodide at the F-Area Seepage Basin - 20225

The Savannah River Site (SRS) produced tritium, plutonium, and special nuclear materials for national defense, medicine, and the space programs. As part of operations, the F-Area Seepage Basins operated until 1988 for the disposition of deionized acidic wastewater from the F Separations Facility. The wastewater contained dilute nitric acid and low concentrations of non-radioactive metals, and radionuclides, with the major isotopes being Cs-137, Sr-90, U-235, U-238, Pu-239, Tc-99, I-129, and tritium. The seepage basins were closed in 1988 and backfilled and capped by 1991. The groundwater emanating from beneath the closed and capped seepage basins is acidic and contains elevated levels of both chemical and radiological contaminants. Releases from the groundwater plumes sourced from the F-Area Seepage Basins have impacted the water quality of Fourmile Branch, which is a small tributary to the Savannah River, a regional water source. A large pump-and-treat system was constructed in 1997 and operated until 2003 in an attempt to capture the releases to Fourmile Branch. The system in F Area and a similar system in H Area were expensive (∼$1.3 M/month) to operate and produced large quantities of radioactive waste, with concentrations of I- 129 too high to be disposed of at the SRS. In 2004, SRS replaced pump-and-treat with a funnel and gate system that along with operation of a base injection system at the gates reduces the flux of contaminants to the wetlands adjacent to Fourmile Branch. The alkaline solution injected into the aquifer neutralizes the acidic plume and immobilizes many of the cationic constituents. However, base injection is not effective in managing the release of iodine-129, an anionic contaminant. To address iodine-129 SRS and the Savannah River National Laboratory developed an in situ technology that uses ultra-fine ground silver chloride (AgCl) as an injectable capture medium for the sequestration of iodine-129. The AgCl amendment has a very small particle size and is designed to be injected into the contaminated aquifer to capture iodine-129. Dissolved iodine-129 forms a stable and highly insoluble solid (silver iodide) upon contact with AgCl. Laboratory studies, a field scale pilot test (2009), and three deployments (2011, 2015 and 2019) of AgCl have been successfully performed at the F-Area Seepage Basins. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Reproducibility of Radiokrypton in Deep Desert Aquifers: Insights from a Decade of Research

Great technical advances have been achieved since the first atom-trap trace analysis (ATTA) -based radiokrypton application in Egypt, where 1 Myr old groundwater was discovered. Beyond advances in ATTA measurement capabilities, including reduction in sample size, analysis duration, and analytical uncertainty, major progress has been achieved over the past two decades in the sample collection and preparation techniques. These advances paved the expansion of ATTA-based noble gas applications to many other aquifers worldwide, illuminating the nature and flow pattern of deep groundwater systems. While the potential of this new analytical technique for old groundwater dating is well recognized, another important aspect yet to be examined is the reproducibility of radiokrypton in aquifers over time, i.e., how representative is a discrete groundwater sample, collected at a specific time and location, for the natural groundwater system? The likelihood of a negative answer is increased by flow-field disturbance in aquifers following massive groundwater abstraction. Here, in this work, we present repeated 81 Kr sampling and measurements in twenty-one sites over Israel, mostly of deep (up to 1 km) wells tapping confined aquifers in the arid to hyperarid Negev desert. The results demonstrate that radiokrypton measurements are indeed reproducible, even in cases where samples were collected as long as nine years apart and from highly productive (∼1 Mm 3 /yr order) pumping wells. Furthermore, many of the repeated measurements in this study (17 out of the 21 sites) were conducted with different ATTA Instruments in two different laboratories using slightly different sampling, preparation, and analysis techniques, yet with an overall good agreement. The consistency in the ATTA-based 81 Kr-dating results over time highlights the robustness of this state-of-the-art technique as a tool to unravel groundwater flow patterns and encourages further applications to many other yet-to-be-explored deep aquifers.

atom-trap trace analysis↗

CY2019 Annual Closure Monitoring Report for Corrective Action Unit 98, Frenchman Flat, Underground Test Area, Nevada National Security Site, Nevada (January 2019–December 2019), Revision 1

Three types of monitoring are performed for CAU 98: water quality, water level, and institutional control. These are monitored to determine whether the URs remain protective of human health and the environment, and to ensure that the regulatory boundary objectives are being met. Monitoring data will be used in the future, once multiple years of data are available, to evaluate consistency with the groundwater flow and contaminant transport models because the contaminant boundaries calculated with the models are the primary basis of the UR boundaries. Six wells were sampled for water-quality monitoring in 2019. Contaminants of concern were detected only in the two source/plume wells already known to contain contamination as a result of a radionuclide migration experiment. Tritium concentrations in both of these wells, RNM-2S and UE-5n, remain above the Safe Drinking Water Act maximum contaminant level of 20,000 picocuries per liter but declined in 2019 as compared to measurements in 2018. All other contaminants of concern are below the minimum detection level plus analytical error. The water-level monitoring network includes 16 wells. Depth to water measured in 2019 is generally consistent with recent measurements for all wells. Many wells continue to exhibit a long-term downward trend in water level, though changes from 2018 to 2019 are minimal. The sharp 2016 decline in water level in Well ER-5-3-2 remains unexplained, with the lower level persisting through 2019. Rising water-level trends continue to be observed in Well ER-5-3 deep piezometer and former water supply Well WW-5A. Water supply Well WW-5B experienced a rise in water level as a result of an absence of pumping in the first part of the year (due to a mechanical problem), whereas water levels declined in WW-4 and WW-4A in response to greater pumping in 2019. Institutional control monitoring confirmed the URs are recorded in U.S. Department of Energy and U.S. Air Force land management systems, and that no activities within Frenchman Flat basin are occurring that could potentially affect the contaminant boundaries. Survey of groundwater resources in basins surrounding Frenchman Flat similarly identify no current or pending development that would indicate the need to increase monitoring activities or would otherwise cause concern for the closure decision. The URs continue to prevent exposure of the public, workers, and the environment to contaminants of concern by preventing use of potentially contaminated groundwater.

54 ENVIRONMENTAL SCIENCES↗

Adaptive Site Management Strategies for the Hanford Central Plateau Groundwater

Adaptive site management (ASM) is a systematic and iterative management approach that can be used to expedite the remediation of large and/or complex sites. ASM is defined as a formal and systematic project or site management approach centered on rigorous site planning and a firm understanding of site conditions and uncertainties, using science and technology to routinely re-evaluate and prioritize site remedial actions and characterization activities. The goal of the approach is to create a framework of structured and continuous planning, implementation, and assessment processes that accommodates new information and changing site conditions to develop effective and efficient cleanup approaches that achieves the required outcome(s) while optimizing costs, cleanup timeframe, and performance. Central to ASM is an evolving conceptual site model (CSM). Over time, incremental reductions in uncertainty associated with the CSM will occur, while supporting continued progress toward site cleanup and closure through remedy optimization and evaluation. ASM has the potential to expedite cleanup for the Central Plateau area at Hanford through a planned and systematic approach for reducing uncertainty with targeted characterization activities, while continuing remediation activities that advance cleanup for key risk-driving contaminants. A core component of cleanup within the Central Plateau is the 200 West Pump-and-Treat (P&T) system. Even with an active P&T remedy, uncertainty exists with respect to plume distributions, total mass in the aquifer, and currently known continuing sources. Additional uncertainty is associated with multiple contaminant source locations in the vadose zone, which have the potential to create new groundwater plumes in the absence of any source control measures, although not all contaminant fluxes to groundwater will result in contaminant concentrations above cleanup levels. Collectively, these uncertainties need to be addressed in the CSM to support effective and efficient site progress toward cleanup goal(s). Other nontechnical factors that may warrant an ASM approach at the Hanford Central Plateau are associated with the formation of operable units (OUs) used to manage cleanup. With the exception of the 200-ZP-1 OU, the three remaining groundwater OUs only have interim action records of decision. Nine vadose zone source area OUs are also in the early stages of the remedial investigation and feasibility study process, with pending characterization and technology identification activities. A set of proposed site objectives for the Central Plateau are provided in this document as an initial consideration/example and basis for discussion for ASM implementation. These example site objectives were selected with the goal of maintaining protectiveness at the Columbia River through confinement of contaminant plumes within an administratively controlled area below existing surface waste sites and waste disposal facilities. Although site decision makers and regulators need to provide concurrence, these site objectives are used in this document to describe the elements of an ASM approach, including selection of interim objectives and a long-term adaptive management plan. Interim objectives are also defined to yield measurable incremental progress toward the overall site goals. This document identifies initial technical considerations for developing an ASM framework for the Central Plateau cleanup decisions. These considerations are intended to facilitate more specific decisions, such as objectives, near- and long-term actions, and performance metrics, to develop an overall approach that maintains protectiveness but recognizes the uncertainty, long timeframe, and technical challenges that need to be considered in selecting, implementing, and managing remediation at the Hanford Central Plateau.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Guidance for Monitoring Passive Groundwater Remedies Over Extended Time Scales

Passive remediation can be appropriate where natural processes and actions such as institutional controls mitigate exposure to contaminated groundwater, achieving remedial action objectives and protectiveness of human health and the environment. Monitored natural attenuation (MNA) is a prevalent passive remediation strategy supported by a regulatory framework and monitoring design guidance. However, long-term passive remedies are usually selected in combination with at least one active remedy, such as source removal, in situ treatment, or pump-and-treat, functioning as a complementary method for achieving remediation objectives and meeting the applicable statutory and regulatory requirements. However, MNA and existing monitoring guidance primarily target situations where the remedial action objectives are met within a few decades. When time scales for passive remediation extend to many decades (50 years or more), a corresponding change in monitoring strategy is needed to adapt to the extended time scale. This document provides guidance for implementing an extended-scale monitoring (ESM) approach appropriate for long-duration passive remediation. Extended-scale is defined in this document with respect to time (i.e., a long duration of remediation) and a large enough physical scale such that downstream receptors will not be impacted within the remediation timeframe. ESM applies to slow-moving groundwater contaminant plumes and emphasizes monitoring primarily for potential exposure pathways. For this approach, the primary monitoring objective is to demonstrate that the plume diminishes before reaching the receptor zone or point of compliance and/or a receptor does not receive concentrations above the compliance limit. While the overall objectives of protecting human health and the environment are the same as for plumes where remediation can occur over a shorter time period, the time scales between decisions are longer and the dynamics of plume evolution are slower. To this end, a scenario-based strategy is described for different plume and source conditions, defining a containment and receptor zones. The containment zone is the area where the risk of exposure to groundwater contamination can be mitigated (e.g., through institutional controls) during the remediation time period. The receptor zone is defined as the area where exposure to groundwater contamination cannot be mitigated and compliance concentration standards must be met. Within the containment zone, slow plume migration may occur, leading to concentrations that exceed compliance standards. However, where distance to the receptor zone is large relative to plume migration and attenuation rate, this approach can be protective of the receptor zone. Selection of a long-duration passive remedy needs to be based on sufficient understanding of contaminant sources, hydrogeology, and contaminant plumes. A strong technical basis, supported by predictive analysis, is recommended to substantiate that contamination is expected to stay within the containment zone during the active remediation and attainment phase of the remedy, and diminish to meet compliance standards within the extended timeframe prior to reaching the receptor zone (e.g., many decades or even centuries). The ESM approach is based on verification of plume behavior and not on detailed plume dynamics. Monitoring is conducted to confirm expected behavior with an emphasis on exposure pathways to verify that plumes remain contained in areas where the protectiveness objectives can be met. ESM should not be adopted if there is significant risk of the plume extending beyond the containment zone. Given the slow movement within the containment zone, less frequent sampling is required relative to approaches used for conventional-scale remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Comparison of the Environmental Effects of Open-Loop and Closed-Loop Pumped Storage Hydropower

Pumped storage hydropower (PSH) capabilities are generally characterized as either open-loop or closed-loop. The U.S. Department of Energy (DOE) defines open-loop PSH as “continuously connected to a naturally flowing water feature,” and closed-loop PSH as “not continuously connected to a naturally flowing water feature.” All the PSH projects constructed in the United States to date are open-loop, so the potential environmental effects of closed-loop systems are not as well documented as the effects of open-loop systems. To address this knowledge gap, the DOE Water Power Technologies Office, under its HydroWIRES Initiative, has prepared this report to: (1) compare the potential environmental effects of open-loop PSH projects with those of closed-loop PSH projects; (2) describe how these effects are being avoided, minimized, or mitigated at existing projects in other countries and proposed projects in the United States; and (3) discuss the relative significance of the environmental issues. The report begins with a brief introduction on the current status of PSH development in the United States. Next, the report describes the current Federal Energy Regulatory Commission (FERC) hydropower licensing process, emphasizing some recent regulatory changes that affect closed-loop PSH development. The report then provides a summary comparison of the environmental effects of constructing and operating open-loop and closed-loop PSH systems and discusses the relative significance of those issues. This comparison and discussion are based on the results of a literature review and a review of FERC licensing records. The literature review includes journal articles, technical reports, and presentations on the environmental effects of PSH systems. It includes literature from the United States as well as countries where closed-loop PSH projects have been constructed. The FERC records review examines the FERC licensing record (e.g., National Environmental Policy Act documents and license orders) to identify the environmental effects anticipated and mitigation measures proposed for six of the closed-loop PSH projects currently licensed or permitted in the United States. For comparison, the FERC records review also discusses the environmental effects and mitigation measures for four open-loop PSH projects proposed or currently operating in the United States. The comparison of effects between open-loop and closed-loop projects is relative; that is, it characterizes the impacts of each project type as generally lower or higher than another project type. The comparison reflects general trends among project types because there are sometimes exceptions to the examples cited. The comparison is based on both spatial (location) and temporal (duration) factors and reflects both the severity and likelihood of effects. The report concludes that the environmental effects of closed-loop PSH projects are generally lower (i.e., more localized and of shorter duration) than those of open-loop PSH projects because they are located “off-stream,” minimizing aquatic and terrestrial impacts, and often have greater siting flexibility than open-loop PSH projects. For certain closed-loop project designs, however, impacts to groundwater may be higher relative to open-loop projects and should be considered in any environmental review.

13 HYDRO ENERGY↗

Vertical Characterization of Flow and Contaminant Concentration in New Hanford Extraction Wells

Effective groundwater remediation should focus on high-concentration, low-permeability zones within the aquifer, as these areas often present significant challenges to contaminant removal. Characterizing the vertical distribution of contamination in an aquifer is therefore critical for optimizing and monitoring pump-and-treat (P&T) systems to meet target cleanup timelines. Flow patterns driven by hydraulic gradients and variations in permeability are described to provide insight into contaminant mass removal from long-screened wells. The objective of this multi-phase work is to provide actionable recommendations for improving remedy performance monitoring and P&T operations, which ongoing evaluations will address. This report summarizes the preliminary results of vertical flow and contaminant distribution monitoring in new extraction wells at the Hanford Site.

54 ENVIRONMENTAL SCIENCES↗

Can Food–Energy–Water Nexus Research Keep Pace with Agricultural Innovation?

The interconnection among food–energy–water (FEW) systems in meeting societal demands is broadly acknowledged. Similarly, competitive or synergistic allocations of water and energy resources for agricultural production, manufacturing, and human consumption are understood, and their economic impacts can be predicted. Far less appreciated and understood are the outcomes of the FEW nexus in response to operation changes in agricultural practices and the associated technological innovations for future generations. Also, the inter-scale and feedback effects of emerging technology-driven resource reallocation and decision-making on FEW systems are largely unknown. For example, how do the agroeconomic feedbacks of intelligent technologies influence the FEW nexus of agricultural production under environmental and demographic changes? How does the necessary water allocation for powering non-powered dams and pumped-storage hydropower generation influence agricultural production and municipal water supply maintenance? How do solar and wind energy farms influence land use for agriculture and the rural economy? In turn, how can the generated solar and wind energy help reduce the cost of groundwater extraction or water desalination?

42 ENGINEERING↗